CN107112545B - Anode for solid oxide fuel cell, method for producing same, and method for producing electrolyte layer-electrode assembly for fuel cell - Google Patents

Anode for solid oxide fuel cell, method for producing same, and method for producing electrolyte layer-electrode assembly for fuel cell Download PDF

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CN107112545B
CN107112545B CN201580062497.2A CN201580062497A CN107112545B CN 107112545 B CN107112545 B CN 107112545B CN 201580062497 A CN201580062497 A CN 201580062497A CN 107112545 B CN107112545 B CN 107112545B
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anode
fuel cell
electrolyte layer
solid electrolyte
oxide
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CN107112545A (en
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野田阳平
真岛正利
俵山博匡
水原奈保
平岩千寻
东野孝浩
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Sumitomo Electric Industries Ltd
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • H—ELECTRICITY
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    • H01M4/88—Processes of manufacture
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    • H01M4/00—Electrodes
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    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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    • H01M4/88—Processes of manufacture
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    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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    • H01M8/02—Details
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    • H01M8/00—Fuel cells; Manufacture thereof
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    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a method for manufacturing an anode capable of improving the output of a solid oxide fuel cell. The method for manufacturing an anode for a solid oxide fuel cell includes: a first step of molding a mixture containing a perovskite oxide having proton conductivity and a nickel compound; and a second step of burning the molded product obtained in the first step at 1100 to 1350 ℃ in an atmosphere containing 50 vol% or more of oxygen to form an anode.

Description

Anode for solid oxide fuel cell, method for producing same, and method for producing electrolyte layer-electrode assembly for fuel cell
Technical Field
The present invention relates to an anode for a solid oxide fuel cell, and more particularly to an improvement in the method of making the anode.
Background
Perovskite oxides having proton conductivity exhibit high conductivity in the intermediate-temperature range, and are a potential material for the production of solid electrolytes for intermediate-temperature fuel cells. In order to sinter the perovskite oxide to form a solid electrolyte, a heat treatment at a high temperature is required.
An anode (fuel electrode) of a solid oxide fuel cell contains a Ni component as a catalyst, and further contains a solid electrolyte to suppress aggregation of Ni component particles and adjust a thermal expansion rate. An anode comprising a solid electrolyte and a Ni component is generally formed by mixing the solid electrolyte and nickel oxide and co-sintering the resulting mixture.
Non-patent document 1 describes that NiO and BaZr are to be contained in airyCe0.8-yY0.2O3-δThe pellets were burned at 1450 ℃ for 5 hours.
Documents of the prior art
Non-patent document
Non-patent document 1: journal of Power Sources 193(2009) pp 400-407
Disclosure of Invention
Technical problem
However, as described in non-patent document 1, when a perovskite oxide is used for the anode and co-sintering is performed at high temperature, nickel oxide aggregates. The particle diameter of nickel oxide increases due to aggregation, the three-phase interface in the anode decreases, and the reaction resistance increases, so that high output cannot be obtained. In contrast, if the co-sintering temperature is lowered to suppress the aggregation of nickel oxide, sintering of perovskite oxide will be difficult to perform, the direct current resistance increases, and thus high output cannot be obtained.
An object of the present invention is to provide an anode capable of improving the output of a solid oxide fuel cell, a method for producing the anode, and an electrolyte layer-electrode assembly for a fuel cell.
Means for solving the problems
One aspect of the present invention relates to a method of manufacturing an anode for a solid oxide fuel cell, the method comprising: a first step of molding a mixture containing a perovskite oxide having proton conductivity and a nickel compound; and a second step of burning the molded product obtained in the first step at 1100 to 1350 ℃ in an atmosphere containing 50 vol% or more of oxygen to form an anode.
Another aspect of the invention relates to an anode for a solid oxide fuel cell obtained by the above method.
Another aspect of the invention relates to a method of manufacturing an electrolyte layer-electrode assembly for a fuel cell, the electrolyte layer-electrode assembly including a solid electrolyte layer and an anode supporting the solid electrolyte layer, the method including:
step A: shaping a mixture comprising a perovskite oxide having proton conductivity and a nickel oxide;
and B: forming a coating film on one of the main surfaces of the molded article obtained in step a with a slurry containing a perovskite oxide having proton conductivity; and
and C: burning the molded article having the coating film thereon at 1100 to 1350 ℃ in an atmosphere containing 50 vol% or more of oxygen gas to produce an anode from the molded article, producing a solid electrolyte layer from the coating film, and integrating the anode and the solid electrolyte layer.
Technical effects
According to the present invention, it is possible to suppress an increase in reaction resistance and/or direct current resistance and increase the output of the solid oxide fuel cell.
Drawings
Fig. 1 is a schematic sectional view of a battery structure including an anode or an electrolyte layer-electrode assembly obtained by a manufacturing method according to an embodiment of the present invention.
Fig. 2 is a schematic sectional view of a fuel cell including the cell structure body of fig. 1.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of a portion of the anode (after reduction) of example 1.
Fig. 4 is an SEM photograph of a portion of the anode (after reduction) of comparative example 1.
Fig. 5 is an SEM photograph of the surface of the solid electrolyte layer of example 1.
Fig. 6 is an SEM photograph of the surface of the solid electrolyte layer of comparative example 1.
Detailed Description
[ description of embodiments of the invention ]
First, the contents of the embodiments of the present invention are listed and explained.
(1) A first embodiment of the present invention relates to a method for manufacturing an anode for a solid oxide fuel cell, the method including: a first step (molding step) of molding a mixture containing a perovskite oxide having proton conductivity and a nickel compound; and
a second step (main combustion step) of combusting the formed article obtained in the first step at 1100 to 1350 ℃ in an atmosphere containing 50% by volume or more of oxygen to form an anode.
To form a solid electrolyte using a perovskite oxide, sintering at a high temperature is required. However, when an anode comprising a solid electrolyte and a nickel compound is manufactured, when a mixture of perovskite oxide and nickel compound is sintered at high temperature, the nickel compound aggregates, and the three-phase interface decreases. In contrast, if the mixture is burned at a low temperature, the aggregation of the nickel compound is suppressed to some extent. However, sintering of the perovskite oxide and the nickel compound does not proceed smoothly, and the direct current resistance of the anode increases.
According to one embodiment of the invention, in burning a mixture of perovskite oxide and nickel compound, the burning is performed at 1100 ℃ to 1350 ℃ lower than in the prior art. Therefore, it is possible to suppress aggregation of the nickel compound and to suppress an increase in reaction resistance due to a decrease in the three-phase interface. Further, since the mixture is burned in an oxygen-rich atmosphere containing 50% by volume or more of oxygen, sintering (co-sintering) of the perovskite oxide and the nickel compound proceeds smoothly despite the low temperature. Therefore, an increase in the anode direct-current resistance can be suppressed.
Therefore, when the anode obtained in this embodiment is used, the output of the solid oxide fuel cell can be increased. The anode obtained by the manufacturing method according to one embodiment of the present invention is used for a Proton Ceramic Fuel Cell (PCFC).
(2) The perovskite oxide preferably has AXO3A crystal structure wherein the A site comprises Ba and the X site comprises Ce and Y. When such an oxide is used, high proton conductivity can be obtained even at a low temperature range, i.e., about 400 to 600 ℃, which is advantageous in reducing the operating temperature of the fuel cell.
(3) The volume ratio of nickel compound to perovskite oxide in the mixture (═ nickel compound/perovskite oxide) is preferably from 50/50 to 75/25. When the volume ratio is within the above range, aggregation of the nickel compound can be more easily suppressed.
(4) In the second step, the molded product is preferably burned at 1200 to 1350 ℃ in an atmosphere containing 80 vol% or more of oxygen. In this case, the sintering of the oxide and the nickel compound proceeds smoothly, and the effect of suppressing the aggregation of the nickel compound can be further improved.
(5) The mixture may further comprise a cross-linking agent. And the above manufacturing method may further include, after the first step and before the second step: a step of removing the crosslinking agent (a step of decrosslinking) by heating the molded product at 450 ℃ or higher and less than 800 ℃. At this time, the moldability of the mixture can be improved, and since the step of decrosslinking reduces the crosslinker residue in the anode, the degradation of the anode performance is suppressed.
(6) After the first step and before the second step, the manufacturing method may further include: and a step of calcining the molded article at 800 ℃ or higher and lower than 1100 ℃ (calcining step). The calcination carried out before the main combustion step (second step) can further increase the degree of sintering of the oxides and nickel compounds.
(7) Another embodiment of the present invention relates to an anode for a solid oxide fuel cell obtained by the above production method. According to this anode, aggregation of the nickel compound is suppressed, and the degree of sintering of the perovskite oxide and the nickel compound is high. Therefore, an increase in the reaction resistance and/or the direct current resistance is suppressed, and the output of the fuel cell is improved.
(8) Another embodiment of the present invention relates to a method for producing an electrolyte layer-electrode assembly for a fuel cell, the electrolyte layer-electrode assembly including a solid electrolyte layer and an anode supporting the solid electrolyte layer. The method comprises the following steps:
step A: shaping a mixture comprising a perovskite oxide having proton conductivity and a nickel oxide;
and B: forming a coating film on one of the main surfaces of the molded article obtained in step a with a slurry containing a perovskite oxide having proton conductivity; and
and C: burning the molded article having the coating film thereon at 1100 to 1350 ℃ in an atmosphere containing 50 vol% or more of oxygen gas to produce an anode from the molded article, producing a solid electrolyte layer from the coating film, and integrating the anode and the solid electrolyte layer.
According to this embodiment, an electrolyte layer-electrode assembly (anode-supporting solid electrolyte layer) capable of increasing the output of the solid oxide fuel cell can be obtained.
[ details of the embodiments of the present invention ]
Specific examples of embodiments of the present invention will be described with reference to the accompanying drawings. The scope of the present invention is defined not by these illustrative embodiments but by the scope of the appended claims, and is intended to cover all modifications and equivalents of the meaning and scope of equivalents of the claims.
[ method for producing Anode for solid oxide Fuel cell ]
The first step (molding step) and the second step (main combustion step) are performed to form an anode. The step of removing the crosslinking agent (decrosslinking step) and/or the calcining step may be performed after the first step and before the second step, as necessary. If a decrosslinking step and a calcining step are performed, it is preferable to perform the calcining step after the decrosslinking step. Each step is described in detail below.
(first step (Forming step))
In the molding step, a mixture containing a perovskite oxide and a nickel compound is molded into a specific shape. Mixing and molding can be carried out using known methods. The shape of the molded product may be determined according to the fuel cell, and may be, for example, a pellet shape, a disk shape, or a sheet shape.
The perovskite oxide used has proton conductivity. For example, materials known for use in the anode of a fuel cell may be used. The perovskite oxide has AXO3Crystal structure (also including AXO)3-δCrystal structure, where δ represents oxygen ion vacancy concentration), the a site preferably includes Ba, and the X site preferably contains at least one selected from Ce, Zr, and Y. AXO3The crystal structure is similar to that of CaTiO3The crystal structure of (1). The ionic radius of the A site element is larger than that of the X site element.
Specific examples of perovskite oxides include BZY (BaZr)1-x1Yx1O3-δ,0<x1≤0.5)，BCY(BaCe1- x2Yx2O3-δ,0<x2 is less than or equal to 0.5), and BZCY (BaZr)1-x3-y1Cex3Yy1O3-δ,0.5<x3<1,0<y1 is less than or equal to 0.5). These oxides may be used alone or in combination. A portion of the Ce, Zr, and/or Y atoms occupying the X site may be substituted with other elements (e.g., other lanthanides). In the above perovskite oxidePreferably, the a site comprises Ba and the X site comprises Ce and Y. Specifically, BCY is preferable.
In the perovskite oxide, the oxygen ion vacancy concentration can be more than or equal to 0 and less than or equal to 0.15 or more than or equal to 0 and less than or equal to 0.11.
Examples of nickel compounds that can be used include hydroxides, salts (inorganic acid salts such as carbonates), and halides. Oxides of nickel, such as nickel oxide (NiO), are preferred. These nickel compounds may be used alone or in combination.
The volume ratio of the nickel compound and the perovskite oxide in the mixture (═ nickel compound/perovskite oxide) may be in the range of 40/60 to 80/20, for example, preferably in the range of 50/50 to 75/25, more preferably in the range of 55/45 to 70/30. When the volume ratio is within the above range, it is possible to easily increase the degree of sintering during combustion and effectively suppress aggregation of the nickel compound.
The mixture may contain other metal compounds than perovskite oxides and nickel compounds, for example, metal compounds (oxides and/or carbonates) of groups 2 to 4 of the periodic table of elements, such as barium oxide, barium carbonate, cerium oxide, zirconium oxide, yttrium oxide, as required. These metal compounds may be used alone or in combination.
The mixture further comprises a cross-linking agent. The crosslinking agent improves the moldability of the mixture. Examples of the crosslinking agent include materials known for use in electrodes of fuel cells. Examples thereof include polymer crosslinking agents, cellulose derivatives such as cellulose (cellulose ethers), vinyl ester resins (including saponified vinyl ester resins such as polyvinyl alcohol), acrylic resins, and waxes such as paraffin wax. The crosslinking agent may be, for example, 1 to 15 parts by mass or 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the perovskite oxide and the nickel compound.
The mixture may contain a dispersion medium such as water and/or an organic solvent (e.g., hydrocarbon such as toluene, alcohol such as ethanol and isopropanol, and carbitol such as butyl carbitol acetate), as desired. The mixture may contain additives such as surfactants and/or deflocculants (e.g., polycarboxylic acids), as desired.
In the molding step, a mixture obtained by mixing these raw materials may be granulated and then molded as necessary. If necessary, the granulated material may be pulverized and then molded.
(De-crosslinking step)
When the mixture containing the crosslinking agent is molded in the molding step, the crosslinking agent remaining in the molded product is preferably removed in the decrosslinking step. The removal of the crosslinking agent can suppress the degradation of the anode performance.
In the decrosslinking step, the shaped article is heated to remove the crosslinking agent. In the decrosslinking step, the heating may be performed at a temperature at which the crosslinking agent is decomposed at a high temperature or the like to be removed and the aggregation of the nickel compound is avoided (preferably, at a temperature at which the sintering of the perovskite oxide and the nickel compound is not performed). The heating temperature may be selected depending on the kind of the crosslinking agent, and is, for example, 450 ℃ or higher, 500 ℃ or higher, or 700 ℃ or higher. The heating temperature is preferably lower than the calcination temperature and/or the main combustion temperature, and may be lower than 800 ℃, for example.
(calcination step)
The shaped article obtained in the shaping step or the decrosslinking step is calcined in a calcination step before the main combustion step. The calcination step is carried out at a temperature lower than that of the main combustion step. When the calcination step is carried out, the calcination temperature is preferably higher than the temperature of the decrosslinking step. Performing the calcination step can improve the operability and/or processability of subsequent steps.
The calcination temperature is preferably 800 ℃ or more and less than 1100 ℃, or 900 ℃ to 1050 ℃.
The calcination may be carried out in air or, as in the main combustion step, in an oxygen-rich atmosphere. The oxygen content range of the calcining atmosphere may be selected from the same range as the oxygen content of the main combustion step.
The calcination may be carried out at normal pressure or at elevated pressure.
(second step (main burning step))
In the main burning step, the molded article obtained in the molding step (or the decrosslinking step or the calcining step) is burned. In this process, it is important to combust the shaped object at a relatively low temperature and in an oxygen-rich atmosphere. When combustion is performed under the above conditions, the degree of sintering of the perovskite oxide and the nickel compound can be increased and aggregation of the nickel compound can be suppressed.
The main combustion is performed in an atmosphere containing 50% by volume or more of oxygen. The oxygen content in the main combustion atmosphere is preferably 80% or more, or may be 90% by volume or more. The oxygen content in the atmosphere is 100 vol% or less. The main combustion is preferably performed in an atmosphere having an oxygen content of 100 vol%. When the main combustion is performed in the above-described oxygen-rich atmosphere, the perovskite oxide and the nickel compound can be efficiently sintered even at a low temperature. The balance of the atmosphere for the main combustion is, for example, an inert gas such as nitrogen or argon, or air (or a constituent of air).
The main combustion temperature is 1100 ℃ to 1350 ℃, preferably 1200 ℃ to 1350 ℃, more preferably 1250 ℃ to 1350 ℃. When the main combustion temperature is lower than 1100 ℃, sintering is insufficient and direct current resistance increases. When the main combustion temperature is higher than 1350 deg.c, the aggregation of the nickel compound increases. In either case, it is difficult to improve the output.
The main combustion may be carried out at normal pressure or at high pressure.
As described above, the anode is formed by the first step and the second step (according to need, a decrosslinking step and/or a calcining step is further performed).
The obtained anode has a porous structure in which a composite oxide of a perovskite oxide (solid electrolyte material) and nickel oxide (NiO) as catalyst components, and the like are formed. The anode is used as an anode of a solid oxide fuel cell (specifically, PCFC). An anode installed in the fuel cell oxidizes a supplied fuel such as hydrogen gas to perform a reaction of releasing protons and electrons (oxidation reaction of the fuel).
In the anode obtained by the above-described manufacturing method, aggregation of the nickel compound is suppressed as compared with the anode of the related art, and therefore the particle size of the produced nickel oxide is small, so that the nickel oxide is more uniformly dispersed in the anode. Therefore, the three-phase interface in the anode can be increased, and an increase in reaction resistance can be suppressed.
According to the above embodiment, the average particle diameter of the nickel oxide in the anode can be reduced to a low level, for example, 0.5 to 3 μm or 0.5 to 2 μm.
The average particle diameter of the nickel oxide can be calculated by, for example, taking an SEM photograph of a part of the anode, measuring the diameters of equivalent circles (circles having the same area as the particle cross section) of a plurality of (for example, 50) particles included in a certain area region, and averaging the results. Alternatively, the average particle size of the nickel oxide may be estimated based on an SEM photograph of the anode after the nickel oxide contained in the anode is reduced to Ni. Specifically, in the SEM photograph of the anode portion after reduction, the outer contour of the nickel particles and the voids surrounding the nickel particles (voids formed by reduction to remove oxygen) can be regarded as constituting the shape of the original nickel oxide. For such nickel particles and voids surrounding them, the diameter of the equivalent circle of the portion can be measured, and the average of the diameters measured at a plurality of positions (for example, 50) is calculated to determine the average particle diameter of the nickel oxide. The average value thus calculated is not much different from the average value obtained from the circle-equivalent diameters of the nickel oxide portions as described above, and can be taken as the average particle diameter of the nickel oxide.
The anode thickness may range, for example, from about 10 μm to 2mm, or may be from 10 to 100 μm. The thickness of the anode may be increased so that the anode serves as a support for supporting the solid electrolyte layer. In this case, the anode thickness may be selected from a range of about 100 μm to 2 mm.
[ method for producing electrolyte layer-electrode Assembly ]
In a manufacturing method according to another embodiment of the present invention, an electrolyte layer-electrode assembly (which may also be simply referred to herein as an assembly) is manufactured, which includes a solid electrolyte layer and an anode supporting the solid electrolyte layer.
As described above, the method of manufacturing the joined body includes the step a (molding step), the step B (coating film forming step), and the step C (main burning step). Step a and step C correspond to the first step (molding step) and the second step (main combustion step) of the above-described anode production method. After step a and before step C, a decrosslinking step of removing the crosslinking agent and/or a calcining step may be further included. The de-crosslinking step may be performed between step a and step B, and/or between step B and step C. The calcination step may be carried out between step a and step B, and/or between step B and step C, and is preferably carried out between step a and step B. In the following description, each step is described more specifically.
(step A (Molding step))
The molding step is the same as the first step (molding step) of the above-described method for manufacturing an anode, and therefore, a description of the first step may be cited here.
(decrosslinking step (first decrosslinking step))
When the mixture containing the crosslinking agent is molded in the molding step, it is preferable to remove the crosslinking agent remaining in the molded product in the decrosslinking step (first decrosslinking step). The first decrosslinking step is the same as the decrosslinking step in the anode production method, and therefore the above description of the decrosslinking step can be cited here.
Even when a mixture containing a crosslinking agent is used in the molding step, it is not necessary to perform a decrosslinking step (first decrosslinking step) between the molding step and the coating film forming step, and a decrosslinking step (second decrosslinking step) may be performed between the coating film forming step and the main burning step.
(calcination step)
In the calcination step, the molded article obtained in the molding step or the first decrosslinking step is calcined. The calcination step may be performed under the conditions of the calcination step in the anode production method. When the calcination step is performed, the operability and/or workability of the subsequent step can be improved.
(step B (coating film formation step)
In the coating film forming step, a coating film as a precursor of the solid electrolyte layer is formed on the molded article obtained in the molding step, the first decrosslinking step, or the calcining step. A coating film is formed on one of the main surfaces of a molded article with a slurry containing a perovskite oxide having proton conductivity. The coating film can be formed by a known method using a known coater or screen printer.
The perovskite oxide in the slurry may be appropriately selected from the examples explained in the first step. The perovskite oxide used in the coating film forming step may be the same as or different from the perovskite oxide used in the mixture in the molding step. Since the thermal expansion coefficient of the anode and the thermal expansion coefficient of the solid electrolyte layer at the time of combustion can be adjusted to be close to each other, the use of the same oxide is advantageous in suppressing warping or separation.
The slurry may further contain a metal compound selected from the examples illustrated in the first step.
The slurry may further contain a crosslinking agent. The crosslinking agent may be appropriately selected from the examples described in the first step. The amount of the crosslinking agent may be, for example, 10 to 300 parts by mass, or 100 to 200 parts by mass, relative to 100 parts by mass of the perovskite oxide.
The slurry may contain a dispersion medium such as water and/or an organic solvent (as exemplified in the first step), as necessary. The slurry may contain additives such as surfactants and/or deflocculants (polycarboxylic acids, etc.) as needed.
After the coating film is formed, the molded article and the coating film thereon may be dried as necessary.
The coating amount of the slurry may be appropriately adjusted so that the thickness of the solid electrolyte layer obtained by burning the coating film is, for example, in the range of 1 to 50 μm, preferably 3 to 20 μm. When the thickness of the solid electrolyte layer is within this range, the resistance of the solid electrolyte layer is preferably suppressed to a low level.
(decrosslinking step (second decrosslinking step))
In order to suppress the deterioration of the solid electrolyte layer, when the coating film contains a crosslinking agent, it is preferable to perform a decrosslinking step (second decrosslinking step) of removing the crosslinking agent after the coating film forming step and before the main burning step. When the crosslinking agent is used in the molding step and the first decrosslinking step is not performed, a second decrosslinking step may be performed to remove the crosslinking agent remaining in the coating film and the crosslinking agent remaining in the molded article; also, the degradation of the anode performance can be suppressed.
The conditions of the second decrosslinking step may be appropriately set according to the kind of the crosslinking agent contained in the coating film and/or the kind of the crosslinking agent contained in the molded article. More specifically, the decrosslinking step may be performed by appropriately selecting from the conditions described in the decrosslinking step in the anode production method.
(step C (main burning step))
In the main burning step, the molded article and the coating film thereof obtained in the coating film forming step or the second decrosslinking step are burned in a relatively low-temperature and oxygen-rich atmosphere. Due to the main combustion step, the formed article is converted into an anode, and the coating film is converted into a solid electrolyte layer. This results in a joined body in which the anode and the solid electrolyte layer are integrated.
The conditions for performing the main combustion step may refer to the conditions described in the main combustion step (second step) in the anode production method. The solid electrolyte layer formed in the main combustion step has a function of conducting only protons generated in the anode to the cathode in the fuel cell.
Fig. 1 is a schematic sectional view of a battery structure including an anode or a junction body obtained by a manufacturing method according to an embodiment of the present invention.
The battery structure 1 includes a cathode 2, an anode 3, and a solid electrolyte layer 4 interposed therebetween. The anode 3 and the solid electrolyte layer 4 are integrated to form an electrolyte layer-electrode assembly 5.
The thickness of the anode 3 is larger than that of the cathode 2, and the anode 3 serves as a support for supporting the solid electrolyte layer 4 (or the battery structure 1). The embodiments described in the figures are not limiting. The thickness of the anode 3 does not have to be larger than the thickness of the cathode 2. For example, the thickness of the anode 3 may be approximately equal to the thickness of the cathode 2.
When the anode 3 or the joined body 5 is manufactured by the manufacturing method according to the embodiment of the invention, an increase in the reaction resistance and/or the direct current resistance of the anode 3 is avoided, and the output of the fuel cell can be increased.
Fig. 2 is a schematic sectional view of a fuel cell (solid oxide fuel cell) including the cell structure body shown in fig. 1.
The fuel cell 10 includes: a battery structure 1; a separator 22 including an oxidizing agent passage 23, the oxidizing agent being supplied to the cathode 2 of the cell structure 1 through the oxidizing agent passage 23; and a separator 52 including a fuel passage 53, through which fuel is supplied to the anode 3 through the fuel passage 53. In the fuel cell 10, the cell structural body 1 is sandwiched between the separator 22 on the cathode side and the separator 52 on the anode side.
The oxidant passage 23 of the cathode-side separator 22 faces the cathode 2 of the cell structure 1. The fuel passage 53 of the anode-side separator 52 faces the anode 3.
The oxidant passage 23 includes: an oxidant inlet through which an oxidant flows; and an oxidant outlet through which water produced by the reaction, unused oxidant, and the like are discharged (both not shown). One example of an oxidizing agent is an oxygen-containing gas. The fuel passage 53 includes a fuel gas inlet into which fuel gas flows and an outlet for unused fuel and H generated in the reaction2O,N2,CO2Etc. (both not shown). Examples of the fuel gas include hydrogen gas, methane, ammonia gas, and carbon monoxide gas.
The fuel cell 10 may further include a cathode-side current collector 21 interposed between the cathode 2 and the cathode-side separator 22, and an anode-side current collector 51 interposed between the anode 3 and the anode-side separator 52. The cathode-side current collector 21 has a function of dispersing the oxidant gas introduced into the cathode 2 through the oxidant passage 23, in addition to the current collecting function, to supply the oxidant gas to the cathode 2. The anode-side current collector 51 has a function of dispersing the fuel gas introduced into the anode 3 through the fuel passage 53 in addition to the current collecting function to supply the fuel gas to the anode 3. In this regard, each current collector preferably has a sufficiently air-permeable structure. The current collectors 21 and 51 are not essential components of the fuel cell 10.
Since the fuel cell 10 contains a proton-conducting solid electrolyte, the fuel cell 10 can function at an intermediate temperature range of less than 700 ℃, preferably about 400 ℃ to 600 ℃.
(cathode)
The cathode has a porous structure capable of absorbing and ionizing oxygen molecules. On the cathode 2, a reaction (reduction reaction of oxygen) occurs between the oxygen ions and the protons conducted by the solid electrolyte layer 4. The oxidizing agent (oxygen gas) introduced from the oxidizing agent passage is ionized to generate oxygen ions.
The material of the cathode may be, for example, a material known for a cathode of a fuel cell. In particular, compounds containing lanthanides and having a perovskite structure (e.g., ferrierite, manganite, and/or cobaltite) are preferred. Among these materials, a material further containing strontium is more preferable. Specific examples include lanthanum strontium cobalt ferrite (LSCF, La)1-x4Srx4Fe1-y2Coy2O3-δ,0<x4<1,0<y2<1, δ -oxygen ion vacancy concentration), lanthanum strontium manganite (LSM, La)1-x5Srx5MnO3-δ,0<x5<1, δ ═ oxygen ion vacancy concentration), and lanthanum strontium cobaltate (LSC, La)1-x6Srx6CoO3-δ,0<x6 ≦ 1, δ ═ oxygen ion vacancy concentration).
For these perovskite oxides, the oxygen ion vacancy concentration δ may be 0 ≦ δ ≦ 0.15 or 0 ≦ δ ≦ 0.11.
The cathode 2 may contain a catalyst such as Pt from the viewpoint of promoting the reaction between protons and oxides. A catalyst may be mixed with the above materials and the resulting mixture may be sintered to obtain the catalyst-containing cathode 2. The thickness of the cathode 2 is not particularly limited, and may be about 5 to 40 μm.
The cathode may be formed by a known method. The cathode can be fabricated in a similar manner as the anode. If necessary, a crosslinking agent, an additive, and/or a dispersion medium may be added at the time of manufacturing the cathode, as in the case of manufacturing the anode. These components may be appropriately selected from examples regarding the anode.
A buffer layer may be formed between the cathode 2 and the solid electrolyte layer 4 as necessary.
(separator)
When two or more cell structures are laminated to form a fuel cell, for example, the cell structure 1, the cathode-side separator 22, and the anode-side separator 52 are laminated to constitute one unit. For example, two or more cell structures 1 may be connected in series with each other by separators provided with gas passages (oxidant passage and fuel passage) on both sides.
Examples of separator materials include heat-resistant alloys such as stainless steel, nickel-based alloys, chromium-based alloys from the viewpoint of electrical conductivity and heat resistance. Among them, inexpensive stainless steel is preferable. Since the operating temperature of the PCFC is about 400 to 600 ℃, stainless steel may be used as a material of the separator.
(Current collectors)
Examples of the structure used as the cathode-side current collector and the anode-side current collector include a metal porous body containing silver, a silver alloy, nickel, a nickel alloy, or the like, a metal mesh, a stamped metal, and an expanded metal. Among them, a metal porous body is preferable because of its light weight and gas permeability. Specifically, a metal porous body having a three-dimensional network structure is preferable. The three-dimensional network structure is a network structure formed by three-dimensionally connecting rod-like or fibrous metals constituting the porous metal body. Examples thereof include sponge-like structures and nonwoven-like structures.
The porous metal body may be formed by coating a porous resin body having continuous pores on the metal. After the metal coating treatment, the resin inside is removed to form the cavities inside the skeleton of the metallic porous body, thereby constituting a hollow structure. An example of a commercially available porous metal body having such a structure is "Celmet" of nickel, manufactured by sumitomo electrical industries co.
The fuel cell can be produced by a known method using the anode or the electrode-electrode assembly obtained by the above production method.
Examples
The present invention will be specifically described below with reference to examples and comparative examples which do not limit the scope of the present invention.
Example 1
(1) Manufacture of battery structure
A battery structure is manufactured by:
mixing BCY (BaCe)0.8Y0.2O3-δ(δ ≈ 0.1)) and NiO were mixed with a crosslinking agent (Celuna WF-804 and Celuna WF-610, manufactured by kyoto grease limited), an additive (Celuna D-305, manufactured by kyoto grease limited), and an appropriate amount of ethanol, and the resultant mixture was pelletized. The volume ratio of BCY to NiO is 40: 60. Relative to 100 parts of BCY and NiO, a crosslinking agent andthe amounts of the additives were 7.00 parts by mass and 0.54 part by mass, respectively. The resulting granules were shaped into disk-like granules using a die having a diameter of 22mm under a force of 20 kN.
The particles were heated at 750 ℃ for 10 hours to carry out the decrosslinking step. The resulting pellets were heated at 1000 ℃ for 10 hours to effect calcination.
Containing BCY (BaCe) by screen printing0.8Y0.2O3-δ(δ ≈ 0.1)), ethyl cellulose (crosslinking agent), a surfactant (KAOCER 8110, manufactured by kawang corporation), and an appropriate amount of a slurry of butyl carbitol acetate were coated on one of the main surfaces of the calcined particle to form a coating film. The amount of the crosslinking agent and the amount of the surfactant were 152.3 parts by mass and 1.52 parts by mass, respectively, with respect to 100 parts by mass of BCY.
The particles and the coating film thereof were heated at 750 ℃ for 10 hours to remove the crosslinking agent contained in the coating film. After removing the crosslinking agent, the particles and the coating film were heated in an atmosphere of 100 vol% oxygen at 1300 ℃ for 10 hours to perform a main burning step. Thereby obtaining an electrolyte layer-electrode assembly in which a solid electrolyte layer is integrally formed on one of the main surfaces of the anode. The thickness of the solid electrolyte layer of the joined body measured by a scanning electron microscope was 10 μm. The total thickness of the anode and the solid electrolyte layer measured with a vernier caliper was about 1.4 mm.
Formulating a cathode slurry comprising LSCF (La)0.6Sr0.4Fe0.8Co0.2O3-δ(δ ≈ 0.1)) powder, a surfactant (MALIALIM (TM) manufactured by NOF corporation), and an appropriate amount of solvent (toluene and isopropyl alcohol). The cathode slurry was coated on the surface of the solid electrolyte layer of the obtained joined body, and heated at 1000 ℃ for 2 hours to form a cathode (thickness: 10 μm). Thereby forming a battery structure.
(2) Manufacture of fuel cells
A platinum slurry was applied to the cathode and anode surfaces of the battery structure obtained above, and a platinum mesh was attached to form a current collector. A stainless steel cathode side separator provided with an oxidant passage was laminated to the cathode side current collector. A stainless steel anode-side separator provided with a fuel passage was laminated to an anode-side current collector, thereby producing a fuel cell 10 as shown in fig. 2.
(3) Evaluation of
In the production of the above battery structure, SEM photographs of the surface of the solid electrolyte layer formed were taken before the cathode was formed. The battery structure obtained as described above was used to determine the output density, the average particle diameter of the nickel compound, and the reaction resistance in the following steps.
(a) Output density
The cell structure was hydrated in a humid atmosphere at 600 ℃ for 24 hours. The hydrated battery structure was used to measure the output density at varying current densities and determine the maximum value of the output density.
(b) Average particle diameter of nickel compound
After the output density was measured in the above (a), an SEM photograph of a part of the anode in the battery structure was taken. The anode state is: the NiO is reduced to Ni and voids are formed due to the reduction to remove oxygen. In the SEM photograph of the part, the outer contours of the Ni particle and the surrounding void part were regarded as the contours of the NiO particle, and the diameter of the equivalent circle of each contour was measured at 50 randomly selected positions. The average of the results was calculated to calculate the average diameter of the nickel compound. From the results, the average particle size of NiO in example 1 was 1.5. mu.m.
(c) Reaction resistor
The AC impedance was measured under the conditions of an open state and operation temperatures of 500 ℃, 600 ℃, and 700 ℃ to determine the direct current resistance of the entire battery structure. In this process, a current value and a voltage value were measured at a battery voltage lower than the open circuit voltage by about 0.2V, and the total resistance of the battery structural body was determined from the current value and the voltage value. The direct current resistance of the entire battery structure is subtracted from the total resistance of the battery structure to determine the reaction resistance of the entire battery structure.
Comparative example 1
A cell structure and a fuel cell were produced as in example 1, except that the main combustion step was performed at a temperature of 1400 ℃ and in air. The output density and the average particle diameter were evaluated in accordance with example 1. As a result, the average particle size of NiO was 3.3. mu.m.
Example 2
A cell structure and a fuel cell were fabricated as in example 1, except that the ratio of BCY to NiO was changed to 30:70 (volume ratio). The output density and the average particle diameter were evaluated in accordance with example 1.
The results of examples and comparative examples are shown in table 1. Examples 1 and 2 are a1 and a 2. Comparative example 1 is B1.
[ Table 1]
Figure GDA0002232754440000161
As shown in table 1, the reaction resistance of the examples was low and the output was high as compared with the comparative examples.
Fig. 3 and 4 are SEM photographs of a portion of the anode formed in example 1 and comparative example 1, respectively. As shown in these figures, the particle diameter of the nickel compound of example 1 is small and aggregation of the nickel compound is suppressed as compared with comparative example 1.
Fig. 5 and 6 are SEM photographs of the surfaces of the solid electrolyte layers formed in the manufacturing process of the battery structures in example 1 and comparative example 1, respectively. As shown in these photographs, a solid electrolyte layer having a dense and uniform mass was formed in the examples, as compared with the comparative examples. This is considered to be due to the inhibition of nickel aggregation in the anode.
In the above examples, the results obtained when the oxygen concentration was 100% and the main combustion temperature was 1300 ℃ were illustrated. However, as long as the oxygen concentration is 50% to 100% and the main combustion temperature is in the range of 1100 ℃ to 1350 ℃, the same or similar results as in examples 1 and 2 can be obtained. From the viewpoint of increasing the degree of sintering, the oxygen concentration is more preferably 80% to 100%, and the main combustion temperature is more preferably 1200 ℃ to 1350 ℃.
Industrial applicability
The anode electrolyte layer-electrode assembly obtained by the manufacturing method according to the embodiment of the invention provides a high output and good proton conductivity. They are therefore suitable for medium-temperature fuel cells (proton-conducting fuel cells, PCFC) which operate at temperatures below 700 ℃.
List of index symbols
1: battery structure
2: cathode
3: anode
4 solid electrolyte layer
Electrolyte layer-electrode assembly
10 fuel cell
21,51 current collector
22,52 separator
23 fuel path
Oxidant passage 53

Claims (8)

1. A method of making an anode for a solid oxide fuel cell, the method comprising:
a first step of molding a mixture containing a perovskite oxide having proton conductivity and a nickel compound; and
a second step of burning the molded article obtained in the first step at 1100 to 1350 ℃ in an atmosphere containing 50 vol% or more of oxygen to form an anode.
2. The method of manufacturing an anode for a solid oxide fuel cell as claimed in claim 1, wherein the perovskite oxide has AXO3A crystal structure, wherein the a site comprises Ba and the X site comprises Ce and Y.
3. The production method for an anode for a solid oxide fuel cell according to claim 1 or 2, wherein a volume ratio of the nickel compound to the perovskite oxide in the mixture is 50/50 to 75/25.
4. The method for manufacturing an anode for a solid oxide fuel cell according to claim 1 or 2, wherein in the second step, the shaped article is burned at 1200 ℃ to 1350 ℃ in an atmosphere containing 80 vol% or more of oxygen.
5. The manufacturing method of an anode for a solid oxide fuel cell according to claim 1 or 2, wherein the mixture further comprises a crosslinking agent; and is
After the first step and before the second step, the manufacturing method further includes: a step of removing the crosslinking agent by heating the molded product at 450 ℃ or higher and less than 800 ℃.
6. The manufacturing method of an anode for a solid oxide fuel cell according to claim 1 or 2, further comprising, after the first step and before the second step: a step of calcining the molded article at 800 ℃ or higher and lower than 1100 ℃.
7. An anode for a solid oxide fuel cell obtained by the method of claim 1 or 2.
8. A method for manufacturing an electrolyte layer-electrode assembly for a fuel cell, the electrolyte layer-electrode assembly comprising a solid electrolyte layer and an anode supporting the solid electrolyte layer, the method comprising:
step A: shaping a mixture comprising a perovskite oxide having proton conductivity and a nickel oxide;
and B: forming a coating film on one of the main surfaces of the molded article obtained in step a with a slurry containing a perovskite oxide having proton conductivity; and
and C: burning the molded product having the coating film at 1100 to 1350 ℃ in an atmosphere containing 50 vol% or more of oxygen gas to produce the anode from the molded product, producing the solid electrolyte layer from the coating film, and integrating the anode and the solid electrolyte layer.
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Engineering of porosity, microstructure and electrical properties of Ni–BaCe0.9Y0.1O2.95 cermet fuel cell electrodes by gelled starch porogen processing;Gilles Taillades;《 Microporous and Mesoporous Materials》;20110423(第145期);92页实验部分 *
Performance and stability of SOFC anode fabricated from NiO–YSZ composite particles;Takehisa Fukui;《Journal of Power Sources》;20020402(第110期);27页实验部分 *
Takehisa Fukui.Performance and stability of SOFC anode fabricated from NiO–YSZ composite particles.《Journal of Power Sources》.2002,(第110期), *

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JP2016100196A (en) 2016-05-30
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